Shaped resins



United States Patent SHAPED RESINS James 0. Koehler, Parma, Ohio, and Headlee Lamprey,

Lewiston, N.Y., assignors to Union Carbide Corporation, a corporation of New York No Drawing. Filed Mar. 5, 1957, Ser. No. 643,935

2 Claims. (Cl. 260-23) This invention relates to additives designed to improve the shaping of resins and plastics, and toforming methods using said additives.

Plasticizers of one type or another normally are incorporated in synthetic resins to increase their extrusion rates and to provide required properties in the finished article. Thus, for example, acryl nitrile rubbers which are used to aid in the extrusion of vinyl chloride type resins, also impart oil and grease resistance to these resins. Dimethyl phthalate, triphenyl and trioctyl phosphates are plasticizers often compounded with cellulose acetate and ethyl cellulose. In general, the exact amount and type of plasticizer or lubricant used depend on the resin formulation, the processing conditions and the physical properties required of the finished products. As a result, no additive compound or class of compounds may be said to function as a universal plasticizer or stabilizer for all resins.

The main object of this invention, therefore, is to provide plasticizers and stabilizers which are effective in all resinous systems.

An equally important object of this invention is to provide resin compositions having improved extrusion rates and superior physical properties, owing to the incorporation therein of certain organo-metallic derivatives of tin, lead, silicon and zirconium.

Another object of this invention is to provide improved resin extruding and injection molding processes.

The present invention by means of which the foregoing objects are realized is based on the discovery that small percentages of organo-metallic derivatives of tin, lead, silicon and zirconium markedly reduce the viscosity and surface tension of resins and plastics, thereby permitting faster shaping at lower temperatures and pressures, while also improving the physical properties of the finished shapes.

The organo-metallic compounds which modify resins and plastics as above indicated, are selected from the group consisting of the acylates of silicon, tin and lead; and the aminoalcohol andpolyhydric alcohol derivatives of tin, lead, silicon and zirconium.

More specifically these additives are:

(1) Metal carboxylates having the formula V (2) Metal aminoalcohol derivatives having the formulae I H [(RO) M[OC H4N(R')2]4 (HO CR"') j.

2,985,604 Patented May 23, 1961 substituted alkyl group having from to 18 carbon atoms; x may be from 0 to 3; and (4-x). For example:

-(3) Metal polyhydric alcohol derivatives having the formula y equal to or less than wherein M represents silicon, zirconium, tin or lead; R is an aryl, aralkyl, alkaryl or alkyl group having from 1 to 18 carbon atoms; R is H, OH or an alkyl or substituted alkyl radical; R" is H or an alkyl or substituted alkyl and R is an alkalene group and x is a number from 1 to 3. For example:

The above compounds may be prepared by any suitable method, e.g., the metal carboxylates can be prepared by reacting an organic ester having the formula M(OR') with an aliphatic acid having the formula RCOOH, where R is a group having from 10 to 18 carbon atoms, followed by the vacuum distillation of the alcohol by-prodnet. The metal aminoalcohol salt suitably can be prepared by refluxing an organic ester having the formula (OR) M with an aminoalcohol. The resultant product then is shaken with a long chain aliphatic acid. To prepare the metal polyhydric alcoholates, an organic ester having the formula (RO) M is refluxed with a dehydroxy alcohol to provide the final product by transesterification.

The additives of the invention are described in greater detail together with their mode of preparation in the copending applications of H. Lamprey and J. O. Koehler, Serial No. 578,782, filed April 17, 1956, and Serial No. 629,797,,filed December 21, 1956.

In the practice of the present invention, from 0.01 percent to 3.5 percent by weight of the above compounds are incorporated in typical resin formulations priorto the working thereof. Such incorporation may be elfected generally in any known manner conventionally used to introduce additives or modifiers in resins.

The effect of some of these compounds on the surface tension of certain liquid resins, as determined with a Du Nouy tensiometer is given in TableI below.

TABLE I v. Surface Tensionn (D mes/cm!) Surfactant and Amount Used Epoxy Phenolic Polyesin Resin styrene None 55. 3 46. 3 32. 5 Isopropoxystearoxy Zirconate: 0.017 50. 9 42. 6 31. 0 1% 46. 9 38. 9 30. 9 Isopropoxystearoxy Silicate:

The lowering of the viscosity of certainresins' occasioned by the incorporation the'reinof'pnepercefitgof" certain additives, as determined Witha Brookfield vis-- cosimeter, is given in Table- II.

TABLE H For thermosetting resins the how number may be expressed as the number of inches of material extruded viscosity at O 1 o ti i Percent through a inch orifice in two minutes at 275 F. and V I Lowering 1400 p.s.i. Relative effectiveness of the various additives in Vis- Restn Type I N0 Additive w w cosity 7 expressed in terms of the length of the phenolic resln 1% A 1 1% B extruded through a inch orificein the indicated time, E temperature and pressure is expressed in Table IV below.

y. V M ii Eliiii." TABLE IV 48 Styrene-acrylate. Length of thermosetting phenolic resin extruded in 2 1 Additive A is Dlethoxy-di-(triethanolamine)-silicate. Additive B is minutes at F and 1400 P- Isopropoxy stearoxy polysilicate.

As illustrative of the successful practice of the inven- Admve i cii .t ii o r i s tion, six additive compounds of the organo-metallic classes above indicated were incorporated in typical vinyl None 2.14 and phenolic resins. The effects of these additives on the ggi gggfi;ggifi iggg gfig fifif 5%: flow value of thermosetting phenolic and thermoplastic %%]lj iit%fiethgii%gg g)' glya% lg Qi %t--N :6fe--t- 2g 2% vinyl resins were measured- 1% iniiiiix diiniisnoisiinihindie-N31 In the case of thermoplastic vinyl resins, the resin was divleete 9 ground through 10 mesh by the use of a Wiley rotary 1% Emmy Steam polysmcate 21 knife mill. Samples were prepared for measurements by adding /2 grain of each of the additives to separate 50 gram portions of the mill resin, followed by mixing with 25 The effect of the additives of the invention on injecthe aid of a mortar pestle. Additional mixing occurred tion molding of Vinylite, a copolymer of vinyl chloride when the test specimens were injection molded at a temand vinyl acetate having a softening point ranging from perature of 325 F. to make pre-formed slugs inch 140 F. to 170 F. polyethylene and ethocel, a thermoin diameter, and one inch in length for use in flow plastic ethyl cellulose having amelting point ranging from measurements. 200 F. to 210 F. wasdeterinined. In each case the The thermosetting phenolic resin samples were preminimum permissible molding pressure was reduced from pared by adding /2 gram of each additive to separate 50 20 percent to 25 percent by the use of 1 percent of the gram p rt s of the resin. Test specimens inch in additives. More important than the reduction in perdiameter and 1 inch in length Were preformed at room rnissible pressure was the striking improvement in quality mp r t re at a pr r of 00 psi. Flow test of the molded articles obtained with the aid of the addimeasllremellts Were Performed in a modified ROSSitives. In each case the molded articles were completely Peakes apparatus, a constant force, vertical-orifice type free of imperfections or chips. machine eonsieting essentially of n Orifiee,b1eek, charge It was also determined that the addition of a small chamber, ram and a pressure system. A split cone conamount of the additive components greatly increased the taining a vertical orifice inch in diameter and 2% adhesion of resins to waxes. The procedure used to inches in length was clamped on to a steam heated block. make this determination was to take plastic rods of Within the block, below the orifice and concentric with known cross-section and with smooth faces exactly 110 it, was arranged the charge chamber. The ram was so mal to the rod length; to cement these rods together with arranged that it applied pressure to the charge chamber molded candelilla wax containing'the additives; and to from the bottom thereof, forcing material into the orifice. measure, on a tensile test machine, the force required to Preseurewas pp y a mechanical 5Y$tem S0 arranged break the resin-wax bond, and pull the rods apart. Table f thepfessul'e PP to the ram'was varlablerto 1 V below summarizes the eflect of 2 percent additions of 111511 desll'ed P Heat l SuPphed by Steam Passmg the additives of the invention on the adhesion of candelilla through a reducmg valve @4 the block- Temperamre wax to resins. Depending upon the kind of wax involved, g controllednby regulatmglstefm pi'essure' b fin d from 1 percent to upwards of 3.5 percent by weight of Flow value for .thermop astic' resms may 3 e the additives will operate satisfactorily to increase the as the number of seconds required for the material to dh f th 7 flow a specified number of inches. Relative effectiveness 7 a eslon o e of the various additives of the invention expressed in TABLE V the number of seconds (mean) required. for the thermoplastic vinyl resin to flow 4% inches through a /s inch ,Breabpomtm PM orifice at300 F. and 1400 psi. is summarized in Table III b 610W. 7 V Additive Used in the Wax N V i ylon Lucite Poly- TABLE ,III Styrene Extrusion rates of thermoplastic vinyl resin at 300 F. None 82 77 66 and 1400 p.s,i, pressure 7 Tetra-(2-ethylhexanediol)-silicate 189 224 82 Diisopropoxy (Z-ethylhexanediol) -slli- Time, Dit 1i6lii iri"iiii2ii 'nii3 sfiis Additive Used (1 percent in each case) 5: gfiggage 408 434 ir s 2 25" V V 4 75 N,N-dlstearate 449 286 66 Sec Sec.

None 43 84 16.4 r v Dlethoxy-di-(triethanolamine)-sillcate. V 35 .755 8.0 Lucite 1s polymerized thermoplastic methyl methaiiii lffiff fi iiiilfif ffil filp-.-" n is" 16.4 70 eerylate having a Softening Point between and Di-(triethoxysilpxyyglyceryl oleate 40 77 14.7' 240 F V V V 3e as 8.0 Another important. eflect of the organo-metallic comig gfi g g 9 35 55 h pounds of the invention connected with their surface t y st r r i i e 0 '74 2.0 active behavior is their effect on the extrusion rates of carborL-resin 'mixtures, as indicated in:Tab1e .VI below.

TABLE VI Extrusion and baking of 35:100 resin-cake mixes 1 Extrusion Extrusion Temper- Pressure, Apparent Percent ature, C. p.s.i.g. Density Rod Quality Surfactant of Baked Rods (low values are desired) 85 700 1. 48 Poor (die drag). 90 200 1.51 Excellent. 90-98 110 1. 48 Do. 144 800300 1. 21 Poor.

l Resin used was phenolic, thermosetting resin containing approximately '10-20 percent of hexamethylene tetramine.

2 Conventional summer oil presently used for die lubrication; data given for comparison with our surfactant.

3 Rod did not cure; abnormally low density obtained.

Carbon filled resins having 100 parts of coke per 35 parts of resin containing 0.4 part of isopropoxy stearoxy polystannate per 100 parts of resin, extruded at pressures equal to A to /5 of those observed for coke-resin mixes containing no additive. The rods containing the additives were excellent in appearance, and exhibited bake densities equal to or higher than those of control rods.

From the disclosure given hereinabove, it will be apparent that the objects of the invention have been attained, and that there has been provided in accordance therewith, a series of organic compounds exhibiting surface active behavior in resinous systems.

What is claimed is:

1. A shapable, solid, organic material selected from the group consisting of the epoxy resins, the phenolic resins, styrene, styrene acrylate polymers, polystyrene, polyethylene and ethyl cellulose, modified in properties by the incorporation therein of from 0.01 percent to 3.5 percent by weight of at least one additive selected from the group consisting of the metal carboxylates having the wherein M is a metal selected from the group consisting of silicon, tin and lead, 'R is a member selected from the group consisting of the aryl, alkaryl, aralkyl, alkyl and substituted alkyl radicals having from to 18 carbon atoms, R' is a member selected from the group consisting of the aryl, alkaryl, aralkyl, alkyl and substituted alkyl groups having from 1 to 18 carbons and x is a number ranging from 1 to 3; the metal aminoalcohol carboxylic acid salts having the formula:

wherein M is a metal selected from the group consisting of silicon, zirconium, tin and lead, R is a member selected from the group consisting of the aryl, alkaryl, aralkyl, alkyl and substituted alkyl radicals having from 1 to 18 carbon atoms, R is a member selected from the group consisting of hydrogen, aryl, alkaryl, aralkyl, alkyl and substituted alkyl groups having from 1 to 4 carbon atoms, R" is a member selected from the group consisting of the alkyl and substituted alkyl groups having from 10 to 18 carbon atoms, x is a number ranging from 0 to 3, and y is a number not greater than (4x) and the metal polyhydric alcohols having the formula:

RI (RO),M(OCHz(. 7-ROH)4-X wherein M is a metal selected from the group consisting of silicon, zirconium, tin and lead, R is a member selected from the group consisting of the aryl, aralkyl, alkaryl, and alkyl groups having from 1 to 18 carbon atoms, R is a member selected from the group consisting of hydrogen,

6 hydroxyl and the alkyl and substituted alkyl radicals, R is a member selected from the group consisting of hydrogen and the alkyl and substituted alkyl radicals; R is a member selected from the group consisting of the alkylene and substituted alkylene groups and x is a number ranging from 1 to 3.

2. A carbon-filled resin consisting essentially of about 35 parts by weight of a phenolic thermosetting resin containing from 10 to 20 percent by weight of hexamethylene tetramine and about parts of coke, modified in properties by the incorporation therein of from 0.01 to 3.5 percent by weight of at least one additive selected from the group consisting of the metal carboxylates having the formula:

)0011 HO Er a 0 {In 0 R wherein M is a metal selected from the group consisting of silicon, tin and lead, R is a member selected from the group consisting of the aryl, alkaryl, aralkyl, alkyl and substituted alkyl radicals having from 10 to 18 carbon atoms, R is a member selected from the group consisting of the aryl, alkaryl, aralkyl, alkyl and substituted alkyl groups having from 1 to 18 carbons and x is a number ranging from 1 to 3; the metal aminoalcohol carboxylic acid salts having the formula:

wherein M is a metal selected from the group consisting of silicon, zirconium, tin and lead, R is a member se-v lected from the group consisting of the aryl, alkaryl, aralkyl, alkyl and substituted alkyl radicals having from 1 to 18 carbon atoms, R is selected from the group consisting of hydrogen, aryl, alkaryl, aralkyl, alkyl and substituted alkyl groups having from 1 to 4 carbon atoms, R" is a member selected from the group consisting of the alkyl and substituted alkyl groups having from 10 to 18 carbon atoms, x is a number ranging from 0 to 3, and y is a number not greater than (4-x) and the metal polyhydric alcohols having the formula:

wherein M is a metal selected from the group consisting of silicon, zirconium, tin and lead, R is a member selected from the group consisting of the aryl, aralkyl, alkaryl, and alkyl groups having from 1 to 18 carbon atoms, R is a member selected from the group consisting of hydrogen, hydroxyl and the alkyl and substituted alkyl radicals, R" is a member selected from the group consisting of hydrogen and the alkyl and substituted alkyl radicals; R'" is a member selected from the group consisting of the alkylene and substituted alkylene groups and x is a number ranging from 1 to 3, said additives being characterized by their ability to reduce the viscosity and surface tension "of said material, thereby permitting faster shaping thereof at low temperatures and pressures.

References Cited in the file of this patent UNITED STATES PATENTS 2,462,331 Myers Feb. 22, 1949 2,476,307 Klein et al. July 19, 1949 2,615,006 Lane Oct. 21, 1952 2,621,193 Langkammerer Dec. 9, 1952 2,634,285 Rust et al. Apr. 7, 1953 2,681,922 Balt-his June 22, 1954 2,708,203 Haslam May 10, 1955 2,824,114 Bostwick Feb. 18, 1958 2,885,419 Beinfest et al. May 5, 1959 (Other references on following page) 7 OTHER REFERENCES The Chemistry of Synthetic Resins, volumes I and II, by Ellis (1935), pages 346 and 461, published by Reinhold Publishing Co. (New York.)

Dupont'Titanium Organics, Titanium Acylates, Bulletin A 504 2a-1500, 10-53, pages 1-3, Dupont Pigments Dept, Wilmington, Del., 1953.

Chem. and Eng. News, Titanium Organics Show Progress, pages 4226, 4228, October 3, 1955. 

1. A SHAPABLE, SOLID, ORGANIC MATERIAL SELECTED FROM THE GROUP CONSISTING OF THE EPOXY RESINS, THE PHENOLIC RESINS, STYRENE, STYRENE ACRYLATE POLYMERS, POLYSTYRENE, POLYETHYLENE AND ETHYL CELLULOSE, MODIFIED IN PROPERTIES BY THE INCORPORATION THEREIN OF FROM 0.01 PERCENT TO 3.5 PERCENT BY WEIGHT OF AT LEAST ONE ADDITIVE SELECTED FORM THE GROUP CONSISTING OF THE MEATL CARBOXYLATES HAVING THE FORMULA: 